Saturated tetradecyl oxygenated compounds



i I .This alcohol, upen subsequent sulphation. as

Patented July 27, 1937 SATURATED' TETRADECYL OXYGENATED COMPOUNDS Jacob N. Wickert, Charleston, and Benjamin '1. Freure, South Charleston, W. Va., assignors, by mesne assignments, to Union Carbide and Carbon Corporation, a corporation New York No Drawing.

Original application January 5,

1934. Serial No. 705,398. Divided and this application July 25, 1936, Serial No. 92,504

11 Claims. (01. 260-134) This invention relates to the production of certain tetradecyl oxygenated compounds, including a saturated, branched-chain ketone and a saturated, branched-chain alcohol. These compounds have properties adapting them for use as high-boiling solvents in the lacquer and varnish industries, and as starting materials for the production of compounds having valuable detergent, wetting, impregnating, foaming, and emulsifying properties. and useful in the textile, leather, and other industries.

The new tetradecyl ketone may be prepared by the interaction of methylisobutylketone. CHaCO-CHzCH(CH3)2, with ethylhexaldehyde, C4HQ'CH(C2H5) CHO, or with ethylpropylacrolein, C3H1--CH:C(C2H5) CHO, in' the presence of an alkaline compound, for example, an alkali such as caustic potash.

The methylisobutylketone may be prepared by the reaction of acetone with itself in the presence or mild alkalies to form diacetonealcohol. This is then dehydrated and subsequently hydrogenated to produce methylisobutylketone.

The ethylpropylacrolein may be produced by,

condensing butyraldehyde by the addition of one molecule of the buty'raldehyde to the second carbon atom of a like molecule, forming an aldol which then loses the elements of water to form the unsaturated aldehyde, ethylpropylacrolein.

The latter, when hydrogenated, is converted to C4Ho.CH (CaHs) -CHO- CHa-CH(CH3) CHz-CO- -2-methylundeceno'ne-4) (partial hydrogenation) CIHa-C H(CHa) (7ethyl-2-methylundecanone-4) (hydogenat-ign) CI-IaCH(CHa) KGB-CHr-CHz-CHQzHslQHo' (7-ethyl-2-methylundecanol-4) the presence of the slight sulphuric acid acidity.

duced pressure to yield the pure ketone, which with concentrated sulphuric acid, produces the monosulphate of this new tetradecyl alcohol. which is then converted into the salt of the alkylsulphuric ester by treatment with the ap propriate base, such as a caustic alkali solution. The sodium sulphate of this tetradecyl alcohol is a clear, snow-white solid or wax. It is com-e pletely soluble in water and in methanol; and its solutions are effective detergents. Its water solution when shaken produces a voluminous stable foam.

The process is illustrated by the following example:

8.7 kg. of methylisobutylketone was mixed in the cold with 105 grams of caustic potash dissolved in 1750 c. c. of methanol, in a reaction vessel provided with a cooling coil and agitating means. 3.7 kg. of ethylhexaldehyde was then added slowly to the resultant liquid with constant stirring over a period of a half. hour while the temperature was maintained below around 25". C. The reaction product first formed was in the nature of a ketol having the probable composition: v

CH3.CH(CH:) CHaCQCI-IaCI-IOHCH (Cal-i5) Gil-In.

CH3.CH(CH3) CHI.CO.CHICH.CH(C2H5) 0.1a.

After the reaction mixture had been stirred for fifteen hours to complete the condensation', it was made slightly acid to phenolphthalein by means of a. 25% aqueous solution of sulphuric acid. Potassium sulphate separated and was filtered off. The clear filtrate was heated to strip it of unreacted starting material and of.

the water formed when the ketol was heated in The residue consisted chiefly of the unsaturated ketone. This was freed of acid by washing with dilute aqueous caustic soda solution. The re-- sultant neutral solution was distilled under re-' boils at 117 to 120 C. at 7 mm. absolute pressure, and at 256C. at 760 mm. pressure. It has 9. sp. gr. of .842 of 20 C.

This ketone was then charged into a pressure vessel, together with an active nickel catalyst, and was heated to 100 to 125 C. with shaking, in the presence of an excess of hydrogen at 900 to 1000 pounds gauge pressure. Reduction 01' the ketone was continued for sixteen hours until K no further hydrogen was absorbed. The liquid product was then cooled, filtered to remove the catalyst, and the filtrate was purified by fractional distillation. The product will contain varying proportions of a saturated ketone and of the secondary tetradecyl alcohol depending upon the extent of the hydrogenation. The fraction having aboiling point of 101 to 103 C. at 4 mm. pressure, and of 252 to 253 C. at 760 mm. pressure, and a sp. gr. of .834 at 20 C. is a saturated ketone, apparently being 7-ethyl-2 methylundecanone-i. The fraction boiling at 112 to 114 C. at 4 mm., and at 261 to 262 C. at 760,

mm. absolute pressure, has a sp. gr. of .834 at 20 C. and is a secondary tetradecyl alcohol, apbarently 7-ethy1-2 methylundecanol-4.

It is possible to substitute ethylpropylacrolein in the process, in place of the ethylhexaldehyde mentioned in the above example.- For instance, 1.8 kg. methylisobutylketone can be reacted with .75 kg. ethylproplyacrolein in the presence of 300 c. c. of normal methanolic caustic soda solution,

' the conditions under which the reaction and subsequent steps are conducted being the same as set out in the former example. In this modification the unsaturated ketol first formed has the probable composition:

crn-omcno-onp-cownzbut by dehydration is converted to a doubly unsaturated ketone having the probable structure indicated by the designation 7-ethyl-2 methylundecadiene 5,'7,-one 4. This ketone is obtained from the neutral residue from the caustic soda neutralization by distillation of this residue under reduced pressure. It boils at 155 to 160 C. at 22 mm. absolute pressure, and at 270 C. at 760 mm. pressure; and has a sp. gr. at 20? C. of .880.

Hydrogenation of this unsaturated ketone in the manner indicated in the example produces the saturated ketone and secondary tetradecyl phuric acid can vary considerably; and other anhydri-des of organic acids, or the acids themselves or their chlorides, may be substituted for acetic anhydride.

The sulphate thus produced is then treated with 'an aqueous solution of caustic alkali or other base to convert it tothe sodium or other salt. This is then readily salted out of the solution and recovered. The sodium salt of the monosulphate is a clear, snow-white, wax-like. solid. It is completely soluble in water and in methanol and is not precipitated by dilute acids or alkalis. The .various calcium and magnesium salts present in hard waters are not precipitated by this compound, since its calcium and magnesiumsalts are almost as soluble as the sodiupisalt itself. A voluminous stable foam isproduced when its.

watersolution is shaken; and it readily yields a stable lather in sea water or other solution having a high percentage of soluble salts. Its properties therefore render it particularly useful as a wetting and detergent agent.

The following will illustrate "one manner of carrying out the sulphation step of our process: 107 grams (0.5 mol.) of tetradecylalcohol prepared in the manner described supra is slowly added to a mixture of 59.2 grams (.58 mol.) of

' acetic anhydride and 60 grams (.58 1.101.) concentrated (95%) sulphuric'acid during a period of an hour, while maintaining the temperature umes of the solution to one volume of water.

The resultant cloudy solution is extracted with hexane to remove olefine and unreacted alcohol. Upon evaporation of the methonal-water solution to dryness, under'reduced pressure, the detergent sulphate is obtained as a white, dry powder. Other purification methods may be substituted for that here given.

Other proportions of the above reagents besides those recited may be effectively employed in this sulphation step. For instance, good yields of the sulphuric acid ester of the alcohol have been secured, using 1 mol. of acetic a dride, 1 mol. 95% sulphuric acid, and .5 mol. of the tetradecyl alcohol, in the specific manner described supra.

The sulphation of the alcohol also may be effected by other means, as by treatment with chlorosulphonic acid, using carbon tetrachloride or dichlorethyl, ether as solvents; or by a treatment with one or more molar equivalents of around to strength sulphuric acid, at low temperatures, preferably between 0 to 10 C. In the latter case,-the reaction mixture on settling separates into a sulphuric acid layer and an upper layer of acid sulphates. This latter layer is neutralized with aqueous caustic alkali, and extracted with hot water to separate therefrom insoluble impurities. The combined washings are evaporated to dryness under reduced pressure, extracted with methanol to remove sodium sulphate, and again dried,--yielding a clear, white, waxy, water-soluble solid having the desired detergent properties.

The process may be varied by substituting for the methanol in the ketol-forming reaction, other volatile diluents for the ketone and alkali starting materials, which do not take part in the reaction, such as ethanol.

The nickel catalyst can be replaced by other catalysts known to catalyze the hydrogenation of alcohols, as for example, copper, platinum, palladium, and copper chromite.

This application is a division of our application, Serial No. 705,398 for Production of tetradecyl alcohol and intermediates and derivatives thereo filed Jan. 5,1934.

We claim:

- 1; As a new chemical compound, a saturated tetradecyl ketone having the apparent structure designated b the formula mospheric pressure, a gravity of .834 at 7 m I and a boiling point of 252 to 253 c. at 760 m 20 C., and apparently having the composition indicated by the designation 7-ethyl-2-methylundecanol-4.

3. Process of making a tetradecyl oxygenated compound, which comprises reacting methylisobutylketone with a compound selected from the group consisting of ethylhexaldehy-de and ethylpropylacrolein, removing elements of water from the ketol thus produced, and hydrogenating the resultant unsaturated ketone.

4. The process of making a tetradecyl oxygenated compound, which comprises reacting methylisobutylketone with 2 ethylhexaldehyde in the presence of an alkali, removing elementsof water from the ketol thus produced, and hydrogenating the resultant unsaturated ketone.

5. The process of making a tetradecyl oxygenated compound, which comprises methylisobutylketone with 2-ethylhexaldehyde in the presence of a caustic alkali, removing elements of water from the ketol thus produced, and hydrogenating the resultant unsaturated ketone in the presence of a hy-drogenating catalyst.

6. The process of making a tetradecanol-i, which comprises reacting together methylisobutylketone and 2-ethylhexaldehyde, removing elements of water from the ketol thus produced, hydrogenating the resultant unsaturated ketone. distilling the hydrogenated product, and separately recovering the fraction boiling at 261 to 262 C. at 760 mm. pressure. l

'7. The process of producing a tetradecyl oxygenated compound, which comprises reacting together methylisobutylketone and Z-ethylhexaldereaction product, separating therefrom an unsat urated ketone having a boiling point of about 256 'C. at atmospheric pressure, and hydrogenating reacting i the latter in the presence of a hydrogenating catalyst.

8. The process of producing a tetradecyl oxygenated compound, which comprises reacting together in the cold methylisobutylketone and 2- ethylhexaldehyde, eliminating the elements of water from the reaction product, separating therefrom the resultant'unsaturated ketone, and hydrogenating the latter in the presence of a nickel catalyst.

9. The process of producing a tetradecyl oxygenated compound, which comprises reacting together methylisobutylketone and ethylpropyla'crolein, eliminating the elements of water from the reaction product thereby producing an unsaturated ketone having a boiling point of 270 C. at atmospheric pressure, recovering the ketone, and hydrogenating the latter in the presence of a hydrogenation catalyst.

10. The process of making a tetradecyl alcohol, which comprises reacting methylisobutylketone with ethylhexaldehyde in the presence of an alkali, removing the elements of water from the ketol thus produced, and hydrogenating the resultant unsaturated ketone in the presence of a nickel catalyst. 1

11. In the process of making a tetradecyl oxygenated compound, the steps which comprise re-' acting together methylisobutylketone and 2- ethylhexaldehyde, removing the elements of water from the ketol thus produced, hydrogenating the resultant unsaturated ketone., distilling the hydrogenated product, and separately recovering the fraction boiling at 252 to 253 C. at 760 mm. pressure and containing tetradecyl ketone.

JACOB N. WICKERT. BENJAMIN 'r. FREURE. 

